Process of clay treating petroleum distillates



April 20, 1937. E. R. SMOLEY 2,077,494

PROCESS OF CLAY TREATING PETROLEUM DISTILLATES Filed June 30 1933 Patented Apr. 20, 1937 UNITED STATES.

PATENT OFF-ICE VPROCESS'OF CLAY TREATING PETROLEUM DISTILLATES 4 Bugs? R. Smoley, Fort Wayne, Ind., assignor to S da-rd Oil Development Company, a corporation of Delaware Application June so, "1933, Serial No. 678,448

4 Claims.

tain objectionable constituents such as unsaturated compounds which tend to form gum and color imparting bodies and sulfur-containing compounds.

An object of this-invention is to provide a process for substantially removing the objectionable constituents from the petroleum distillates.

This and other objects of the invention will be better understood by reference to the following description takenin connection with the accompanying drawing which illustrates diagrammatically and conventionally one form of apparatus to carry out the invention:

Referring to the drawing, numeral I denotes a furnace setting furnished with a burner 2 for supplying hat. Oil, such as cracking coil distillate, is circulated through a coil 3 in furnace setting I to vaporize the oil and raise the temperature to about 550 to 750 F. and it is passed through pipe 4 into a contacting chamber 5." Non-cracking conditions are maintained at 'all times and the pressure used is about 100 pounds per square inch,

though higher or lower pressures may be used. A layer of clay 6 such as fullers earth or granosil,

of the contacting chamberli to the level I. The depth of the clay layer is about 12 to 18 feet. The outletof pipe 4 in contacting chamber 5 is below the surface of the clay in close proximity to the bottom of contacting chamber 5. The oil vapors after passing through the clay layer are withdrawn from chamber 5 through pipe '8 furnished with valve 8' to a lower part ofnfractionating tower Ill. Pipe 9 arranged with valve 9'is provided for recirculating the oil through coil 3, pipe 4, and contacting chamber 5 in the beginning of the operation to raise the temperature of the oil vapors in the contacting chamber 5 to a desired temperature so that condensation of'the. vapors does not take place in the contacting chamber 5.

Fractionating tower I0 is provided with baflles II in the lower part and bubble cap plates l2 in the part above the baflies. Outlet pipe l3 pro- 55 vided with valve I4 is used to remove the conetc. of 8 to 30,mesh, is maintained in'the bottom densed fractions from the bottom of fractionating tower II) to storage (not shown) after passing. through cooler l5.

The oil vapors passed into tower I0-are fractionated and the heavier fractions condensed and withdrawn through pipe l3. The resulting oil 1 vapors are passed through pipe [6 from the top of fractionating tower l0 to a central point of contacting tower ll. Contacting tower I1 is provided with bubble cap plates l8 anda perforated plate or screen ill at the upper part. A layer of. clay 20 such as fullers earth, granosil, etc. of 8 to.30 mesh is supported upon plate l9. An outlet pipe 2| arranged with valves 22 and 23 is used to withdraw the condensed vapors from the bottom of the tower. The condensed vapors may be passed by means of pump 24 through pipe25 to the top plate of tower H) to serve as reflux. The

condensate may be in part or whole passed through pipe2| to pipe 26 throughcondenser 27 to storage (not shown).

The vapors passed into contacting tower I! are fractionated. The separated vapors are passed "through the clay layer 20 and withdrawn through vapor line 28, condensed by passing through condenser 29 and passed into separating tank 30. A fractionof the condensate in separating tank 1 may be passed through pipe 3| by means of pump 32 to the top of contacting tower I! as reflux .Gases are withdrawn from separating chamber 30 through pipe 33 arranged with valve34. The condensate is removed from separating tank 30 through pipe 35 arranged with valve 36 to storage (not shown). g The pressures .are maintained substantially uniform throughout the system by means of the valves arranged on the outletpipes."

The feed stock is supplied from storage tank r; 31 through pipe 38 provided with pumps 39 and 40. The feed stock may be preheated by circulating through one or both of the coils 4| and 42 placed. in the top of contacting chamber l1 and fractionating tower l0. Valves 43, 44, 45 and 46 are provided on line 38 and are used to regulate the path of flow of the feed stock as it passes from storage tank 31 to accumulating tank4l. Feed stock is passed from accumulating tank 41 through pipe 48 arranged with valve 49 to heating coil 3.

50 Alternately an oilmay be heated to the desired temperature, such as 550 to 750 F., and under pressure of about pounds per square inch and passed through a body of clay maintained in the bottom of a clay contacting chamber similar to tower arefthen withdrawn and condensed.

The invention has the iollowing.advantages-: Objectionable constituentsare removed and the oil is substantially unaffected in that the process does not involve the loss of constituents suitable as components of the desired products. The treated oil is substantially iree from constituents introduced by an acid-alkali refining operation.

, The product is improved particularly as to color and corrosion and as to'stability on exposure to,

sunlight. It has been found that very large yields of motor iuel distillate-may be treated per ton of clay used.- This means that a given charge of clay. will last a very long time. giving continuous operation with aminimum of shut downtime and a minimum clay cost per barrel of finished motor fuel produced. I i

The foregoing description is merely illustrative and various changes and alternative arrange merits may be made. within the scope of the appended claims in which it is my intention to claim. all novelty as broadly as the prior art permits.

Iclaim: 1 1. A process ot'refining a hydrocarbon distillate derived from cracking containing objectionable unsaturates which comprises passing said distil- I late in vapor form after been heated to a temperature above about 550 F. but below crack ing temper'atureand while under superatmospheric pressure in the absence ofadded oxygen through a bed of solid adsorbent material capable of polymerizing objectionable unsaturates present in said distillate, maintaining said bed of 5 solid adsorbent material at a temperature which will avoid condensation of vapors passing therethrough, thereafter passing the vapors so treated into a rec ying zone wherein progressive coolin g'of said v pors is efl'ected and said vapors o undergo extensive fractionalcondensation jand rectification-to separately condense a fraction consisting of, higher boiling constituents of said vapors while retaining the constituents desired in the final distillate .in vapor form, separately withdrawing the condensate so formed, passing cracking temperature and while undersuperatmospherlcpres'ure in the absence of added oxy-' gen through abedot solid adsorbent material capable of objectionable unsaturates 70 present in said distiilate,-'maintaining'said bed of solid adsorbent material at a temperature which will avoid condensation of vapors passing therethrough. thereafter passing the vapors so'treated into a first ir'actionating zone wherein said vapors are subjected to proaressivecooling and rectificathe remaining tractionatedvapors through a'section to condense and separate higher boiling constituents therefrom, separately removing liquid so condensed add separated, passing vapors remaining uncondensed in said iractionating zone into an intermediate point in a second Iractionating zone wherein said vapors are subjected to further progressive cooling to condense a higher boiling traction of said remaining vapors, passing unconde'nsed vapors from said second i'ractionatin zone through a second bed of solid adsorbent material'to eflect further polymerization of objectionable unsaturates and condensing and collectingthe last treated vapors as a desired distillate product.

. 3; A process of refining a hydrocarbon distillate derived from cracking containing objectionable unsaturates'which comprises passing said distilwill avoid condensation of vapors passing there through, thereafter passing the vapors so treated into a rectifying zone wherein progressive cooling ofsaid vapors is effected and-said vapor's'under; go extensive fractional condensation and rectification toseparately condense a fraction consisting of higher boiling constituents oi said vapors while retaining the. .constituents desired in the final distillate in vapor form, separately withdrawing the condensate so formed, passing the remaining fractionated vapors through a second bed of solid fidsorbent material to effect further polymerization" of objectionable unsaturates,

passing a liquid reflux medium through said sec- 0nd bed in bountercurrent contact with vapors passing therethrough to separate said polymers from said vapors and remove polymers former; from said bed and condensing and collecting vapors'from said last-named treatment as a desired distillate product.

. "4, A process of refininga hydrocarbon distillate derived from .cracking containing objectionable unsaturates which comprises passing said distillate in vapor formv after having been heated to a. temperature above about 550 F. but belowcracking temperature and while under superatmospheric-pressure in the absence of added oxygen through a bed of solid adsorbent material capable of polymerizing objectionable unsaturates present in said distillate, maintaining said bed of solid adsorbent material at a temperature which will avoid condensation of vapors passing therethrough, thereafter passing the vapors so treated. into a rectifying zone containing no solid adsorb; ent material wherein progressive cooling or said -,vapors is elected .andrsaidvapors undergo extensive fractional condensation and rectification .to separately condensea iraction consisting of higher boiling constituents of said vapors while retaining the constituents desired in the final distiilate in vapor form, separately withdrawing the condensate; so. formed, passing the remaining fractionated vapors through a second bed o1 solid adsorbent material to 'eifect further polymerization of objectionable 'unsaturatesfand condensing and collecting the resulting treated vapors as the desired distillate product.

means a. 

